Organoelectroluminescent device having a substrate, a negative electrode, an organic electroluminescent layer, a buffer layer containing an adhesion-increasing porphyrinic compound and a cathode electrode

ABSTRACT

A semiconductor device with a substrate, a first electrode on the substrate, at least one of an injection layer or a transporting layer on the first electrode, an adhesion layer on the at least one of an injection layer or a transporting layer, and a second electrode on the adhesion layer.

This application is a continuation application of U.S. application Ser.No. 09/848,282, filed May 4, 2001 (now U.S. Pat. No. 6,663,985), whichis a continuation application of U.S. application Ser. No. 09/178,515,filed Oct. 26, 1998 (now U.S. Pat. No. 6,248,458), which claims priorityfrom Korean Application No. 60534/1997, filed Nov. 17, 1997, KoreanApplication No. 18193/1998, filed May 20, 1998 and Korean ApplicationNo. 37215/1998, filed Sep. 9, 1998, the subject matters of which areincorporated herein by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a semiconductor device.

2. Background of the Related Art

Semiconductor devices can include many different forms. One form allowselectricity to be transformed into light by applying the light to aluminescent material.

Referring to FIG. 1, a related art semiconductor device is shown with afirst electrode 2 formed 20 on a transparent substrate 1, a holeinjecting layer (HIL) 3 and a hole transporting layer (HTL) 4 formed onthe first electrode 2, a luminescent layer 5 formed on the HTL 4, anelectron transporting layer (ETL) 6 and an electron injecting layer(EIL) 7 formed on the luminescent layer 5, and a second electrode 8formed on the EIL 7. Any one or more of HIL3, HTL 4, ETL 6 and EIL 7 maybe omitted, depending on the particular device structure adopted.

Electrons and holes injected into the luminescent layer through thesecond electrode 8 and the first electrode 2, respectively, recombine todecay radiatively. For most semiconductor devices, the charge injectionbarrier is higher for electrons than for holes. It is well known thatthe electron injection barrier may be lowered by employing a low workfunction material for the second electrode 8. However, low work functionmaterials are chemically reactive, which makes it difficult to use suchmaterials for electrodes. Accordingly, such materials are often used asa second electrode after being alloyed with one of more stablematerials, as seen in the examples of Mg:Ag and Al:Li. However, suchalloyed second electrodes are still less stable, more costly to form,and more difficult to deposit in a uniform film as compared to aluminum.

An even more serious problem often encountered with an alloyed secondelectrode of Mg:Ag or Al:Li is the frequent occurrence of cross talk orcurrent leakage between pixels, which may be attributed to the diffusionof Mg or Li ions across organic layers of the device. This problem canbe greatly alleviated if one selects aluminum as a second electrodematerial. However, in the case of aluminum there is a need to improveits poor electron injecting capability. The electron injectingcapability of a high work function second electrode, such as aluminum,can be significantly enhanced by inserting a very thin layer (typically0.3 nm to 1.0 nm) of an electrically insulating material such as LiF,MgF₂ or Li₂O, inserted either between an aluminum electrode and theluminescent layer, or between the aluminum electrode and the ETL (see,for example, IEEE Transactions on Electronic Devices, Vol. 44, No. 8, p1245-1248(1997), the contents of which are incorporated herein in theirentirety).

Li₂O is a particularly interesting material, in this regard, in that itis an electrically insulating material with a very low work function.The work function of alkali metals themselves is very low, and itbecomes even lower when oxidized: for example, work function decreasesfrom 2.1 eV for Cs to about 1 eV for Cs₂O Various alkali metal compoundshave reportedly been used to form an insulating buffer layer for thepurpose of lowering the electron injecting barrier: e.g., Li₂O, LiBO₂,NaCl, KCl, K₂SiO₃, RbCl, and Cs₂O to name a few.

Despite this improvement, the introduction of the insulating bufferlayer poses a challenging new problem, namely, deterioration of adhesionbetween an EL multilayer and aluminum, with consequent reduction of lifetime of the device. Experimental results reveal evidence of pooradhesion either at the buffer layer/aluminum interface or at the ELmultilayer/buffer layer interface. This situation is not unexpected,given the different characteristics of materials involved. In summary,semiconductor devices of the related art have at least two basicdrawbacks, namely, poor adhesion and short life time.

The above information is expressly incorporated by reference in itsentirety herein where appropriate for appropriate teachings ofcompositions useful in the invention, as well as additional oralternative details, features and/or technical background.

SUMMARY OF THE INVENTION

An object of the invention is to solve at least the above problemsand/or disadvantages and to provide at least the advantages describedhereinafter.

An object of the present invention is to provide a semiconductor devicewith a long life time 20 and have high efficiency.

An object of the present invention is to provide a semiconductor device,including a substrate, a first electrode on the substrate, at least oneof an injection layer and a transporting layer on the first electrode,an adhesion layer on the at least one of an injection layer and atransporting layer, and a second electrode on the adhesion layer.

Additional advantages, objects, and features of the invention will beset forth in part in the description which follows and in part willbecome apparent to those having ordinary skill in the art uponexamination of the following or may be learned from practice of theinvention. The objects and advantages of the invention may be realizedand attained as particularly pointed out in the appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

The invention will be described in detail with reference to thefollowing drawings in which like reference numerals refer to likeelements wherein:

FIG. 1 illustrates a cross-sectional view of a related art semiconductordevice; and,

FIG. 2 illustrates a cross-sectional view of a semiconductor device inaccordance with a preferred embodiment of the present invention.

FIG. 3 illustrates a cross-sectional view of a semiconductor device inaccordance with a further preferred embodiment of the present invention.

FIG. 4 illustrates a cross-sectional view of an electroluminescentmultilayer which may include one or more of a hole injection layer, ahole transporting layer, a luminescent layer, an electron injectinglayer, and/or an electron transport layer.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

Referring to FIG. 2, the semiconductor device in accordance with apreferred embodiment of the present invention includes a laminatedstructure of a transparent substrate 21, a first electrode 22, anelectroluminescent (EL) multilayer 23 (which may include one or more ofa HIL, a HTL, a luminescent layer, an EIL, and/or an ETL, wherein the ELmultilayer may be an organic EL multilayer), a second electrode 24, anda protection film 25.

In addition, disposed between the EL multilayer 23 and the secondelectrode 24 may be a layer I 26 and/or a layer II 27, which primarilyserve for improving inter-layer adhesion and electron injection,respectively. The present invention may include only layer I 26, onlylayer II 27 or include both layer I 26 and layer II 27.

In a preferred embodiment of the invention, layer I can include anymaterial, preferably an adhesive material to increase the adhesionbetween surrounding layers. More preferably, layer I includes aporphyrinic compound.

Herein, the term EL multilayer may encompass a plurality of layerscomprising a luminescent layer and typically one or more of the HIL,HTL, ETL, and EIL. Additionally, the EL multilayer is preferably anorganic EL multilayer.

In addition, layer II 27, which may be disposed anywhere in thelaminated structure, preferably between the layer I and the secondelectrode, is designed to improve the electron injection capability andcan include any material, preferably at least one material selected fromthe group consisting of an alkali metal, an alkaline earth metal, and acompound thereof. Exemplary preferred materials for layer II 27 includeLi, Cs, Li₂O, and LiF. The second electrode 24 is formed of a metal orits alloy, most preferably aluminum.

The semiconductor device of the present invention having the layer I 26and the layer II 27 10 thus stacked between the EL multilayer 23 and thesecond electrode 24 shows a substantially prolonged life time as well asa high luminance. The layer I 26 and the layer II 27 may be stacked inthe opposite sequence to that shown in FIG. 2, which results indecreased luminance and life time. The layer I 26 and the layer II 27may have a thickness of from about 0.5 nm to about 50 nm and from about0.2 nm to about 3 nm, respectively.

According to another aspect of this invention, there is provided a meansto improve the life time of a semiconductor device, as well as theelectron injecting capability, by inserting, instead of a dual layer ofthe layer I and the layer II, a mixed layer 28, comprising a mixture ofthe components of layer I and layer II, wherein the mixed layer isinserted between the EL multilayer and the second electrode. The mixedlayer is formed by the co-deposition of(1) at least one first materialselected from the group consisting of compounds of chemical formula Iand (2) at least one second material selected from the group consistingof an alkali metal, an alkaline earth metal and a compound thereof. Theratio of the first and second materials in the mixed layer can be eitherfixed or varied as a function of position, i.e., by forming aconcentration gradient of the first and second materials within themixed layer.

Preferably, the mixed layer may have a thickness of from about 0.5 nm toabout 10 nm. Exemplary preferred materials comprising layer II 27include Li, Cs, Li₂O, and LiF. The second electrode 24 is formed of ametal or its alloy, most preferably aluminum.

In addition, the layer I may include at least one adhesive compound,preferably a porphyrinic compound, which serves principally to improvethe adhesion between the EL multilayer 23 and the second electrode 24,while retaining good electron transporting capability.

Exemplary devices have been fabricated in accordance with the presentinvention, and their performance has been compared with that of relatedart devices: the two devices (A and B) are of the related art, and theother two devices (C and D) represent two embodiments of the presentinvention.

The basic structure of a related art EL device for green emissioncomprises: (1) a first electrode of indium tin oxide (ITO) 150 nm thick,(2) a buffer layer of copper phthalocyanine (CuPc) typically about 10 nmto about 20 nm thick, (3) a hole transporting layer ofN,N′-diphenyl-N,N′-bis(3-methylphenyl)-(1,1′-biphenyl)-4,4′-diamine(TPD) typically 30 nm to 50 nm thick, and (4) an emitting layer oftris(8-hydroxy-quinolate)aluminum (Alq₃) typically about 40 nm to about60 nm thick.

The device A has a second electrode of aluminum formed directly on theEL multilayer (device structure: ITO/CuPc/TPD/Alq₃/Al); while the deviceB has a layer of Li₂O about 1 nm thick between the EL multilayer and thesecond electrode (device structure: ITO/CuPc/TPD/Alq₃/Li₂O (1 nm)/Al).The device C has a structure of ITO/CuPc/TPD/Alq₃/CuPc(2 nm)/Li₂O(1nm)/Al, while the device D has a structure of ITO/CuPc/TPD/Alq₃/Li₂O(1nm)/CuPc(2 nm)/Al. In short, the layer-forming sequence of Li₂O(1 nm)and CuPc(2 nm) is reversed for the devices C and D. Finally, all deviceshave been encapsulated in an inert atmosphere.

TABLE I lists the voltage measured between a first electrode and asecond electrode, luminance, and life time of the device, with eachsample device subjected to a constant current density of 3 mA/cm².

TABLE I luminance voltage (V) (cd/m²) life time Device A 6 50 short(less than 1 hour) Device B 6 100 short (less than 1 hour) Device C 6150 long (longer than 2000 hours) Device D 8 130 intermediate (roughly100 hours)

The life time quoted in TABLE 1 represents the time by which luminancedrops to half the initial value for each device. It is apparent fromTABLE 1 that the devices C and D of the present invention have superiorlong-term stability as compared with the devices A and B of the relatedart. This result may be explained as follows: Li₂O shows poor adhesionto both Alq₃ and aluminum (e.g., device B). In addition, a 1 nm-thicklayer of Li₂O does not form a complete and uniform layer, but rather atype of island structure. As a result, in device C, a part of the CuPclayer is apparently in direct contact with aluminum through voids in theLi₂O layer, which significantly contributes to enhancing the adhesion ofthe EL/metal interface and consequently the life time of the device,such as device C. The copper ion in CuPc is probably responsible for therelatively strong bonding between CuPc and aluminum. Compared to deviceC, device D exhibits a higher driving voltage because of the raisedelectron-injection barrier, due to the presence of CuPc between Li₂O andaluminum, and consequently device D exhibits a shorter life time due tothe increased electrical and thermal stress.

According to another embodiment of the invention, there is provided ameans to improve the life time as well as the electron injectingcapability of a semiconductor device, by inserting, instead of a duallayer of the layer I 26 and the layer II 27 in FIG. 2, a mixed layercomprising layer I 26 and layer II 27 between the EL multilayer and thesecond electrode.

The mixed layer is formed by the co-deposition of (1) a first material,which preferably includes at least one porphyrinic compound; and (2) asecond material comprising at least one of an alkali metal, an alkalineearth metal, and/or a compound thereof. The use of the mixed layerimproves adhesion, but deteriorates electron injection slightly. Themixing ratio between the two groups of materials can be fixed throughoutthe layer, or varied as a function of position (i.e., to form aconcentration gradient of the components within the layer).

According to a preferred embodiment, the mixed layer has a concentrationgradient wherein: (1) the relative concentration of the second materialcomprising at least one of an alkali metal, an alkaline earth metal, andcompounds thereof is zero at the interface with the EL multilayer, andunity at the interface with the second electrode, and varying graduallyin between; and (2) the relative concentration of the first material,preferably including porphyrinic compounds is unity at the interfacewith the EL multilayer, and zero at the interface with the secondelectrode, and varying gradually in between. The thickness of the mixedlayer is preferably in the range of from about 0.5 nm to about 10 nm.

Advantages of semiconductor devices of the present invention include thefollowing: The insertion of either a dual layer of layer I 26 and layerII 27, or a mixture of the two layers between the EL multilayer and thesecond electrode leading to significant improvements in the long-termstability as well as the luminance of a semiconductor device, whereinlayer I 26 comprises an adhesive material, and layer II 27 preferablyincludes at least one of an alkali metal, an alkaline earth metal,and/or a compound thereof.

U.S. Pat. No. 6,248,458 B1 is hereby incorporated herein by reference inits entirety. The foregoing embodiments and advantages are merelyexemplary and are not to be construed as limiting the present invention.The present teaching can be readily applied to other types ofapparatuses. The description of the present invention is intended to beillustrative, and not to limit the scope of the claims. Manyalternatives, modifications, and variations will be apparent to thoseskilled in the art. In the claims, means-plus-function clauses areintended to cover the structures described herein as performing therecited function and not only structural equivalents but also equivalentstructures.

1. An organic electroluminescent device comprising: a substrate; a firstelectrode on the substrate; an organic electroluminescent layer on thefirst electrode; a mixed layer on the organic electroluminescent layer,the mixed layer including a first material having at least one of analkali metal, an alkaline earth metal, or a compound thereof, and asecond material having an adhesive material for increasing adhesionbetween the mixed layer and the organic electroluminescent layer; asecond electrode on the mixed layer; wherein a concentration gradient ofthe first material is zero at an interface between the organicelectroluminescent layer and the layer, mixed and the concentrationgradient of the material increases gradually in a direction of aninterface between the mixed layer and the second electrode, and aconcentration gradient of the second material is zero at the interfacebetween the mixed layer and the second electrode, and the concentrationgradient of the second material increases gradually in the direction ofthe interface between the organic electroluminescent layer and the mixedlayer.
 2. An organic electroluminescent device comprising; a substrate;a first electrode on the substrate; an organic electroluminescent layeron the first electrode, the organic electroluminescent layer includes ahole injection layer (HIL), a hole transporting layer(HTL), an electrontransporting layer (ETL), and an electron injection layer (EIL); a mixedlayer on the organic electroluminescent layer, the mixed layer includinga first material having at least one of an alkali metal, an alkalineearth metal, or a compound thereof, and a second material having anadhesive material for increasing adhesion between the mixed layer andthe organic electroluminescent layer; a second electrode on the mixedlayer; wherein a concentration gradient of the first material is zero atan interface between the organic electroluminescent layer and the mixedlayer, and the concentration gradient of the first material increasesgradually in a direction of an interface between the mixed layer and thesecond electrode, and a concentration gradient of the second material iszero at the interface between the mixed layer and the second electrode,and the concentration gradient of the second material increasesgradually in the direction of the interface between the organicelectroluminescent layer and the mixed layer.
 3. The organicelectroluminescent device of claim 2, wherein the mixed layer isprovided between the organic electroluminescent layer and the secondelectrode.
 4. The organic electroluminescent device of claim 3, whereinthe first electrode is provided between the substrate and the organicelectroluminescent layer.
 5. The organic electroluminescent device ofclaim 1, wherein the mixed layer is provided between the organicelectroluminescent later and the second electrode.
 6. The organicelectroluminescent device of claim 5, wherein the first electrode isprovided between the substrate and the organic electroluminescent layer.